Phthalimide containing monoazo dyestuffs

ABSTRACT

MONOAZO DYESTUFFS FREE FROM SULFONIC ACID GROUPS ARE PREPARED WHICH ARE VALUABLE NEW PIGMENT DYESTUFFS CHARACTERIZED BY GOOD FASTNESS TO LIGHT, SLOVENTS AND MIGRATION, AND BY A GOOD THERMAL STABILITY WHEN USED FOR COLORING PAPERS, LACQUERS, VARNISHES, SYNTHETIC MATERIALS, PIGMENT PASTE AND PRINTING COLORS. THE DYESTUFFS CORRESPOND TO THE GENERAL FORMULA WHERE R1 AND R2, INDEPENDENTLY OF ONE ANOTHER, MEANS HYDROGEN, AN OPTIONALLY SUBSTITUTED ALKYL, ARALKYL OR ARYL RADICAL; X STANDS FOR AN OXYGEN OR SULFUR ATOM R FOR NH; K1 IS THE RADICAL OF A MONOFUNCTIONAL COUPLING COMPONENT; R IS A SUBSTITUENT; AND M IS AN INTEGER FROM 0-3.   -N(-R1)-R2   WHERE A STANDS FOR AN OPTIONALLY SUBSITUTED ALKYL, ARALKYL, CARBOCYCLIC OR HETEROCYCLIC RADICAL OR FOR THE RADICAL   1,3-DI(O=),2-(A-C(=X)-NH-),(K1-N=N-),(R)M-ISOINDOLINE

United States Patent PHTHALIMIDE CONTAINING MONOAZO DYESTUFFS Walter Horstmann, Cologne, Dietmar Kalz, Leverkusen, .Gerhard Wolfram, Opladen, and Edgar Siege], Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Nov. 26, 1968, Ser. No. 779,225 Claims priority, application Germany, Dec. 6, 1967,

Int. Cl. C09b 29/36 its; (:1. 260-156 I 2 Claims ABSTRACT OF THE DISCLOSURE Monoazo dyestuffs free from sulfonic acid groups are prepared which are valuable new pigment dyestuffs characterized by good fastness to light, solvents and migration, and by a good thermal stability when used for coloring papers, lacquers, varnishes, synthetic materials, pigment paste and printing colors. The dyestuffs correspond to the general formula where A stands for an optionally substituted alkyl, aralkyl, carbocyclic or heterocyclic radical or for the radical where R and R independently of one another, mean hydrogen, an optionally substituted alkyl, aralkyl or aryl radical; X stands for an oxygen or sulfur atom or for NH; K is the radical of a monofunctional coupling component; R is a substituent; and m is an integer from 0-3.

The object of the present invention comprises new monoazo dyestuflt's which are free from sulphonic acid groups and correspond to the formula it K1N=N NII-o-A and a process for their production.

In the Formula I A stands for an optionally substituted alkyl, aralkyl, carbocyclic or heterocyclic radical or for the radical where R and R independently of one another, denote hydrogen, an optionally substituted alkyl, aralkyl or aryl radical; X stands for an oxygen or sulphur atom or for NH; K is the radical of a monofunctional coupling component; R is a substituent and m is an integer from 0 to 3.

Suitable alkyl radicals A are, for example, branched 3,644,405 Patented Feb. 22, 1972 and straight-chain C -C alkyl radicals, such as methyl,

ethyl, propyl, isopropyl or butyl radicals.

Suitable aralkyl radicals are primarily benzyl radicals such as Suitable carbocyclic radicals are, in particular, optionally substituted aryl radicals, especially phenyl radicals or naphthyl radicals, such as or cycloalkyl radicals such as cyclohexyl radicals. Suitable heterocyclic radicals are, for example,

and suitable radicals are, for example, -NH NHCH -NHC H and Examples of substituents R are primarily alkyl groups, such as methyl, ethyl and butyl groups; halogen atoms, such as fluorine, chlorine and bromine; alkoxy groups,

such as methoxy and ethoxy groups; nitro groups and trifiuoromethyl groups.

Suitable radicals K are especially the radicals of 2-hydroxy-naphthoic acid-(3)-ary1ides, acetoacetic acid arylides, pyrazolones-(S and S-aminopyrazoles.

The new azo dyestufis of the Formula I are obtained by reacting azo compounds of the formula I COOH K1N=N o OH M in which K R and m have the same meaning as above, or their anhydrides, semiesters or neutral esters, with compounds of the formula A-d-NH-NIIZ (III) in which A and X have the same meaning as above, in a molar ratio of 1:1, optionally in the presence of suitable condensation agents, in a high-boiling organic solvent, and selecting the components in such a manner that the final dyestutfs are free from sulphonic acid groups.

A group of particularly valuable dyestuffs within the scope of the products of the Formula I are obtained by reacting compounds of the formula COOH )rn in which K R and m have the same meaning as above,

or functional derivatives of these dicarboxylic acids, especially the monoor diesters or anhydrides, with compounds of the Formula III, dyestuffs of the formula )m being formed.

Another process for the production of the azo dyestuffs of the Formula I consists in diazotising amines of the formula R m 9) (VI) in which A, R, X and m have the same meaning as above, in the usual manner and coupling with the coupling components K H. The compounds of the Formula VI are obtained by the reaction of opitonally substituted 3- or 4-nitrophthalic acids or their functional derivatives, with compounds of the Formula III in a high-boiling organic solvent in the presence of acidic condensation agents and subsequent reduction of the resultant nitro compounds.

Preferred dyestulfs are those which are free from sul fonic acid groups and correspond to the general formula where A is selected from the group consisting of alkyl with 1-9 carbon atoms; cyclohexyl; phenyl; phenyl substituted by a member Cl, CH OCH CONI-I or NHOCCH 4 benzyl, benzyl substituted by a member Cl, CH or OCH naphthyl, pyridyl; carbanilino phenylene; carbanilino phenylene substituted by a member Cl or CH benzoylamino phenylene; and benzoylamino phenylene substituted by a member C1 or CH or A is a radical where R and R are selected from the group consisting of H; methyl, ethyl and phenyl; R is selected from the group consisting of alkyl with 14 carbon atoms, fluorine, chlorine, bromine, methoxy, ethoxy, nitro, or trifluoromethyl; m is an integer from 0 to 3; and K is selected from the group consisting of 2-hydroxynaphthoic-acidanilido; wherein the anilido residue of said Z-hydroxynaphthoic-acid-anilido is unsubstituted or contains 1-3 substituents selected from the group consisting of methyl, methoxy, ethoxy, nitro, chloro and acetylamino; 3-methyl-pyrazolonyl-S which is unsubstituted or contains one substituent selected from the group consisting of phenyl, chlorophenyl, methylphenyl, nitrophenyl, carbonamido, and carbomethoxy, acetoacetic acid anilido wherein the anilido residue of said acetoacetic acid anilido is unsubstituted or contains 1-3 substituents selected from the group consisting of chloro, methyl, methoxy, ethoxy and nitro; Z-hydroxynaphthoic acid naphthyl-amido; 2-hydroxy naphthoylamino benzimidazolonyl; 1-phenyl-3- methyl-S-amino-pyrazolyl; acetoacetic acid naphthylamido; acetoacetic acid amino benzimidazolonyl; or acetoacetic acid aminobenzothiazolyl and X is selected from the group NH, S, and O.

The starting dyestuffs of the Formula II or IV are obtained in usual manner by diazotising the optionally substituted aminophthalic acids or their functional derivatives and coupling with monofunctional coupling components. The following diazo components can be used for this purpose, for example:

Examples of suitable monofunctional coupling components K H are:

2-hydroxy-naphthoic 2-hydroxy-naphthoic Z-hydroxy-naphthoic Z-hydroxy-napbthoic 2-hydroxy-naphthoic 2-hydroxy-naphthoic Z-hydroxy-naphthoic 2-hydroxy-naphthoic 2-hydroXy-naphthoic Z-hydroxy-naphthoic anilide, Z-hydroxy-naphthoic anilide, 2-hydroxy-naphthoic chloro -anilide, Z-hydroxy-naphthoic chloro) -anilide,

acid-(3 -anilide,

acid- 3 )-2'-methyl-anilide,

acid- 3 (4'-methyl -anilide, acid- (3 -(2-methoxy) -anilide, acid- 3 4'-rnethoxy -anilide, acid- (3 3 '-nitro anilide,

acid- 3 (2'-chloro -anilide, 'acid- 3 (4'-ch1oro) -anilide, acid- (3 -(2',4'-dimethyl) -anilide, acid- 3 2-methyl-5-chloro acid- (3 -(2-methyl-4'-chloro) acid- 3 (2,5'-dimethoXy-4'- acid-(3 2,4-dimethoxy-5 aceto Z-hydroxy-naphthoic acid- (3 (2-methy1-4'-methoxy) anilide, 2-hydroxy-naphthoic anilide, I 2-hydroxy-naphthoic anilide, 2-hydroxy-naphthoic 2-hydroxy-naphthoic 2-hydroxy-naphthoic 2- hydroxy-naphthoic 2-hydroxy-naphthoic anilide, i 2-hydroxy-naphthoic': acid 3 (4'-acety1amino -anilide, 5 (2',3 hydroxy-n aphthoyl amino -benzimidazolone, 1-phenyl-3methyl-pyrazolbne-S, 1- (4'-chloroplienyl) -3 -methyl-pyrazolone-5, 1- (4-methyl-phenyl -3 -methyl-py razolone-5 1- 3,:nitrophenyl) -3 -methyl-pyrazolone-5, 1-(2'.:chlorophenyl)-3-methyl-pyrazolone5, 1phenyl-pyrazolone-5-carboxylic acid-3-amide, 1-phenyl-pyraz0lone-S-carboxylic acid-S-methyl ester, 1-phenyl3-methyl-5 amino-pyrazole,

acetic acid anilide, I v acetic acid-2-chloro-anilide, acetic acid-2,4:dimethyl-anilide, acetic acid-Z-methyl-anilide, acetic. acid-2,5-dimethoxy-4-chloro-anilide, acetic zicid-Z-methoxy-anilide, acetic .acid -vnaphthyl- 1 )-amide, acetic acid-2:.rnethyl-3-chloro-anilide, acetic acid-Z-methyl-S-chloro-anilide, acetic acid- Z-methylA-chloro-anilide, acetic acid-2,4-dichloro-anilide, acetic acid.-2-nitro-4-ch1oro-anilide, acetic acid-2-nitro-4-methyl-anilide, acetic acid-Z-nitro-4-methoxy-anilide, acetic acid-4-ethoxy-anilide, acetic acid-2-(6-ethoxybenzothiazolyl)-amide,

acid- 3 2-methoxy-5-chloro acid- (2' -methyl-3-chloro acid- (3 -(naphthyl)-( 1') -amide, acid- (3') (naphthyl- (2) )-amide, acid 3 (2'-ethoxy) -anilide, acid- 3 (4-ethoxy) -anilide, acid- 3 (2-methoxy-5-methyl aceto aceto aceto aceto aceto aceto acetoaceto aceto aceto aceto aceto aceto aceto aceto S-acetoacetylamino-b enzimidazolone.

The condensation of azo compounds (II) or (IV) with compounds of the type (111) according to the invention is preferably carried out in a high-boiling organic solvent and in the presenceof dehydrating'agents. The condensation is performed, for example, at an elevated temperature,-generally in the range from 80 C. to 240 0, preferably between 100 C. and 180 C., and, if desired, under pressure;

Compounds (III) which are suitable for the production of azo dyesufis of the Formula I are, for example, semicarbazide, .thiosemicarbazide, aminoguanidine and their substitution products, .forexample,

benzoic' acid hydrazide,

4-chlor6-benzoic acid hydraiide,

'3,4 dichlo'ro -berlzo ic acid hydrazide, '4-metliyl-benzoic acid hydrazide,

4-rnethoxy-benzoic acid hydrazide, 4- carbanilinobenzoic acid hydrazide,

4-(4'-chloro-carbanilino)-benzoic acid hydrazide,

4-(3,4-dichloro-carbanilino)-benzoic acid hydrazide,

4-(2',4',5'-trichloro-carbanilino)-benzoic acid hydrazide,

4-(4'-methyl-carbanilino)-benzoic acid hydrazide,

4-carbamido-benzoic acid hydrazide,

cyclohexane-carboxylic acid hydrazide,

naphthoic acid-Z-hydrazide,

naphthoic acid-l-hydrazide,

nicotinic acid hydrazide,

isonicotinic acid hydrazide,

4-(2',5'-dichloro-carbani1ino)-benzoic acid hydrazide,

4-acetyl-amino-benzoic acid hydrazide,

4-benzoyl-amino-benzoic acid hydrazide,

4-(4-chloro-benzoylamino)-benzoic acid hydrazide,

4-(4-methyl-benzoylamino)-benzoic acid hydrazide,

2,S-dichloro-4-carbamido-benzoic acid hydrazide,

3-carbonamido-benzoic acid hydrazide,

3-carbonamido-4-chloro-benzoic acid hydrazide.

. Organic solvents which are suitable for condensing monoazo dyestuffs (II) or (IV) or their derivatives with compounds (III) are the following solvents boiling above C.: benzene, toluene, xylenes, chlorobenzene, 0-, m-, p-dichlorobenzene, trichlorobenzenes, quinoline, nitrobenzene, glacial acetic acid, cyclohexane, 1,2,3,4-tetrahydro-naphthalene, naphthalene, tetrachloro-ethylene, anisole, diphenyl ether, di-n-butyl ether decaline and mixtures of such solvents. The preferred condensation agents to be added are, for example, acidic dehydrating agents, such as formic acid, acetic acid, propionic acid, anhydrous sodium acetate, zinc chloride, iron(III) chloride, aluminum chloride and boron trifluoride.

The reaction of (II) and (IV), or of their derivatives, with (III) is carried out in a molar ratio of about 1:1, an excess of 10-20% of component (III) being preferably used, in order to achieve a complete conversion.

The products obtainable according to the invention are valuable new pigment dyestuffs which are generally characterised by good fastness to light, solvents and migration and by a good thermal stability in the various substrates. They are used for colouring papers, lacquers and varnishes and synthetic materials, such as e.g. plasticiser-containing polyvinyl chloride, polyethylene and mixed and graft polymers of acrylonitrile-butadiene-styrene, and for the production of pigment pastes and printing colours.

The parts given in the following examples are parts by weight, the temperatures are degrees centigrade.

EXAMPLE 1 9.5 parts of the monoazo dyestufr obtained from diazotised 3-amino-phthalic acid and Z-hydroxy-naphthoic acid- (3)-anilide are heated in a mixture of 225 parts o-dichloro-benzene and 25 parts glacial acetic acid at 110-120 for 1 hour. 4 parts 4-chlorobenzoic acid hydrazide are then added and the same temperature is maintained for a further 4 hours. The pigment is then filtered off with suction at washed with hot o-dichlorobenzene until the runnings are clear, and dried at 80 in a vacuum until the weight is constant. There are obtained 11.5 parts of red pigment of the formula which is fast to light.

To improve the strength of colour, the product is around with the tenfold amount of sodium chloride in a ball mill for 20 hours, the salt is dissolved out with Water, and the product is dried as above.

7 EXAMPLE 2 10.8 parts of the azo dyestufl? obtained from 4-amino- S-methoxy-phthalic acid and 2-hydroxy-naphthoic acid- (3)-(4'-acetylamino)-anilide are heated in a mixture of 225 o-dichloro-benzene and 25 ml. glacial acetic acid at 120 for 2 hours, 6 parts 4-carbani1ino-benzoic acid hydrazide are then added, the temperature of 120 is maintained for a further 15 hours, the product is filtered off with suction While hot, Washed with hot o-dichlorobenzene and methanol, and dried. There are obtained 13.5 parts of 10 a red pigment dyestufl of the formula mc-oo-nrr-Q-rqmp 0 OH EXAMPLE 3 which is very fast to light and solvents.

EXAMPLE 4 9.1 parts of the azo dyestuff obtained from diazotised 3-amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)- anilide are heated in a mixture of 200 parts chlorobenzene and 20 parts glacial acetic acid at 120 for 1 hour, 2.2 parts thiosemicarbazide are then added, and the temperature of 120 is maintained for a further 4 hours. The finished pigment is subsequently filtered ofi with suction at 100, Washed with 250 parts of hot chlorobenzene and 100 parts methanol, and dried at 50 until the Weight is constant. The yield amounts to 10 parts of red pigment of the formula which is fast to solvents.

When the procedure described in the above examples is followed, but the diazo and coupling components and imidisation components of the Formula IEEI there mentioned are replaced with the diazo and coupling components and the imidisation components listed in the following table, then valuable pigment dyestuffs are likewise obtained, which have the specified shades.

Diazo component Coupling component Imidisation component Shade 3-arnino-phthalic acid 2-hydroxy-naphthoic acid- (3) anilide Semicar lde Red. Do ..d0 4-methyl-semicarbazide Red. Aminoguanidine Red. Red. Red. Red. Red. Red. Red. do Red. 2-hydroxy-naphthoie ac1d-(3)-4- Red.

ethoxyanilide.

Thiosemicarbazide Red. 4-chloro-benzoic acid hydrazide" Red. 4-carbamido-benzoic acid hydrazide Red. 4-carbanilino-benzoic acid hydrazidc Red. 4(3-ehloro-ca.rbanilino)-benzoic acid hydrazide..- Red. 4-(3,4-dich1oro-carbanilino)-bcnzoic acid hydrazidm Red. 4-(2,4,5-trichloro-carbanilino)-benzoic acid hydrazidc Red. 4-(4-methyl-carbani1ino)-bcnz0ic acid hydrazidc Red; 4-aceW1amino-bcnzoic acid hydrazide Red. 4-bcnzoylamino-benzoic acid hydrazide Red. Thiosemicarbazide Red.

Semicarbazide Red; 4-earbemidabenzoic acid hydraz Red. 4-(4-ohlorocarbauilino)-benzoic aci Red. 4-acetyla1nino-benzoic acid hydrazidem Red. l-benzoylamino-benzoic acid hydrazide Red. D d 4-(4'-chlor -benzoylamin9)-bcnzoic acid hydrazide Red. Dn dn -carbamhno-benzoic acid hydrazide Red.

TABLEContinued Diazo component Coupling component Imidisation component Shade 3-amino phthalic acid 2-hg d rgxymaphthoic acid-(3)-(4-chloro)- Thiosemicarbazide Red:

Semicarbazide Red.

d-carbanilino-benzoio acid hydrazide. 4-(4-chloro-carbanilino)-benzoic acid hydrazi e... 4-(2,4 ,5-trichloro-carbanilino)-benzoic acid hydrazi e 4-(3,4-dichloro-carbani1ino)-benzoic acid hydrazide 4-acetylamino-benzoic acid hydrazide Do do 4-benzoylamino-benzoic acid hydrazide Red.

Do 2hydroxy-naphi ho1c acid-(3)-(4- 4-chloro-benzoic acid hydrazide Red.

methoxy)-anihde.

Do 4(4-chloro-carbanilino)-benzoic acid hydrazide Red.

Do 4-benzoylamino-benzoie acid hydrazide Red.

Thiosemicarbazide Do.. Do h dr naphthoic acid-(3)-(2- 4-carbonamido-benzoic acid hydrazide -5-chloro)-anilide. D o 4-(4-chloro-carbanilino)-benzoic acid hydrazide Red. Do -do 4-acetylamino-benzoic acid hydrazide Red. Do o Semicarbazide. Red. Do 2-hydroxy-naphtho a Thiosemicarbazide Red.

methoxy)-anilide.

do Acetylamino-benzoic acid hydrazide Red. 4-carbonamido-benzoic acid hydrazide. Red. 4-carbanilino-benzoic acid hydrazide... Red. 4-benzoylamino-benzoic acid hydrazide Red. Thiosemicarbazide Yellow. 4(4-chloro-carbanilino)-benzoic acid hydrazide Do. 4(4 -ch1oro-carbanilino)-benzcic acid hydrazide D0. d-carbonamido-benzoic acid hydrazide Do. Semicarbazide Do.

Thiosemicarbazide Do. 4-carbonamido-benzoic acid hydrazide Do. do 4(4-chloro-carbanilino)benzoic acid hydrazide. D0. Aceto acetic acid-2,4-d1methylan1 1 e 4-carbanilin0-benz0ic acid hydrazide-.. Do. l-phenyl-3-methyl-pyrazolone-5 Thiosemicarbazide Do. 4-chloro-benz0ic acid hydrazi Do. 4-(4 -ch1oro-carbanilin0) benzoic Do. -acetylamino-benzoic acid hydrazide Do. i-benzoylamino-benzoic acid hydrazide Do. Thiosenn'carbazide Red. 4 carbonamido benzoic acid hydraz Red. 4-(4-chloro-carbani lino)benzoic acid hy Red. Do do 4-benzoylamino-benzoic acid hydrazide Red. Do 2-hydfigxymaphthoic acid-(3)-(2 Semicarbazide Red.

am e. Do do 4-carbanilino-benzoic acid hydrazide Red. D0 2-hydfigxy-naphthoic acid-(3)-(4-ethoxy)- 4-(4-ch1oroearbanilino) benzoic acid-hydrazid Red.

am e. D0 do 4-carbonamido-henzoic acid hydrazide Red. Do 5-(2,3'-hydroxy-naphthoylamino)- Thlosemicarbazlde Red.

benzimidazolone.

N-acetyl-hydrazine Red. Benzoic acid hydrazide Red. 4-chloro-benzoic acid hydrazide Red. -carbanilino-benzoic acid hydrazide. Red. Semicarb azide Red. Thiosemicarbazide Red. 4-ch1oro-benzoic acid hydrazide Red. 4-(4-chloro-carbani1ino)benzoic acid hydrazide Red. 4-acetylamino-benzoic acid hydrazide Red. -benzoylamino-benzoic acid hydrazide Red. 4-carbonamido-benzoic acid hydrazide..- Red. d 4-cagbanilino-benzoic acid hydrazide... Ylelow o 0. 4-amino-5-methoxy- .do 4-(4-chlor0-earbanilino) -benzoic acid hydrazide Do.

phthalic acid.

Do 2hydrcxy-naphthoic acid-(3)-(4'-acetyl- 4-carbonamido-benzo1c acid hydrazide Red.

amino) -anilide. Do l-phenyl-3-methyl-pyrazolone-5 4-(2,4',5Qtrichlorocarbanilino) -benzoic acid hydrazide Yellow. Do Acetgiigcetic acid 2,5-dimethoxy-5-chloro- Thiosemlearbazide Do.

am e. 3-amino-phthalic acid. 2-hydrcxy-naphthoic acid-(3)-(2,4- Carbanilino-benzoic acid hydrazide Red.

dimethoxy-fi-chloro) -anilide. Do 2-hydroxy-naphthoic acid-(3) -(4'-acetyl- Red.

amino) -anilide. We claim: -where R and R are selected from the group consisting 1. Azo dyestuifs which are free from sulfonic acid of H; methyl, ethyl and phenyl; R is selected from the groups and correspond to the general formula group consisting of alkyl with 1-4 carbon atoms, fluorine, 0 chlorine, bromine, methoxy, ethoxy, nitro, or trifluoroll methyl; m is an integer from 0 to 3; and K is selected X from the group consisting of Z-hydroxynaphthoic-acid- KPNzN anilido; wherein the anilido residue of said 2-hydroxysubstituents selected from the group consisting of methyl,

(R methoxy, ethoxy, nitro, chloro and acetylamino; 3-methy1- pyrazolonyl-S which is unsubstituted or contains one sub- Where A 15 Selected from the group conslstmg of alkyl stituent selected from the group consisting of phenyl,

223 5 i g i l f gfj gz 3 3? ggg g g chlorophenyl, methylphenyl, nitro phenyl, carbonamido, NHOCCH benzyl benzyl substiulted y A member Cl and carbomethoxy; acetoacetic acid amlido wherein the CH or FE 1 b h 1 f amlido residue of sa1d acetoacetic acid anilido is unsubnap Pym y can am mo P eny stituted or contains 1-3 substituents selected from the carbanilino phenylene substituted by a member C1 or CH group consisting of chloro, meth l methox ethox and benzoylamlno phenylene; and benzoylamlno phenylene nitro; hydroxymaphthoicadglaphthylimido; 2

substituted by a member C1 or CH or A is a radical dmxy naphthoylamino benzimidazolonyl; 1 l.

R1 3 methyl 5 amino pyrazolyl; acetoacetic acid naphfrom the group NH, S, and O.

thylamido; acetoacetic acid amino benzimidazolonyl; or acetoacetic acid aminobenzothiazolyl and X is selected 11 12 2. Monoazo dyestuffs of claim 1 which are free from References Cited sulphonic acid groups and correspond to the formula FOREIGN PATENTS K1-N=III 6,701,983 9/1967 Netherlands 260--152 5 CHARLES B. PARKER, Primar Examiner D. M. PAPUGA, Assistant Examiner (1R)m o0 C1; X-R.

- 10 260-152, 157, 158, 162, 326 N,"558 H '559 H, 559 S, 1332211112? A, X, R, K and m have the same meanmg as 1n 562 106 288; 154 x V 

